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Diamondoid

December 20, 2023

In chemistry, diamondoids are variants of the carbon cage molecule known as adamantane (C10H16), the smallest unit cage structure of the diamond crystal lattice. Diamondoids also known as nanodiamonds or condensed adamantanes may include one or more cages (adamantane, diamantane, triamantane, and higher polymantanes) as well as numerous isomeric and structural variants of adamantanes and polymantanes. These diamondoids occur naturally in petroleum deposits and have been extracted and purified into large pure crystals of polymantane molecules having more than a dozen adamantane cages per molecule.[1] These species are of interest as molecular approximations of the diamond cubic framework, terminated with C−H bonds. Cyclohexamantane may be thought of as a nanometer-sized diamond of approximately 5.6×10−22 grams.[2]

Examples edit

 
Diamondoids, from left to right adamantane, diamantane, triamantane and one isomer of tetramantane

Examples include:

  • Adamantane (C10H16)
  • Iceane (C12H18)
  • BC-8 (C14H20)
  • Diamantane (C14H20) also diadamantane, two face-fused cages
  • Triamantane (C18H24), also triadamantane. Diamantane has four identical faces available for anchoring a new C4H4 unit.
  • Isotetramantane (C22H28). Triamantane has eight faces on to which a new C4H4 unit can be added resulting in four isomers. One of these isomers displays a helical twist and is therefore prochiral. The P and M enantiomers have been separated.
  • Pentamantane has nine isomers with chemical formula C26H32 and one more pentamantane exists with chemical formula C25H30
  • Cyclohexamantane (C26H30)
  • Super-adamantane (C30H36)

One tetramantane isomer is the largest ever diamondoid prepared by organic synthesis using a keto-carbenoid reaction to attach cyclopentane rings.[3] Longer diamondoids have been formed from diamantane dicarboxylic acid.[4] The first-ever isolation of a wide range of diamondoids from petroleum took place in the following steps:[1] a vacuum distillation above 345 °C, the equivalent atmospheric boiling point, then pyrolysis at 400 to 450 °C in order to remove all non-diamondoid compounds (diamondoids are thermodynamically very stable and will survive this pyrolysis) and then a series of high-performance liquid chromatography separation techniques.

In one study a tetramantane compound is fitted with thiol groups at the bridgehead positions.[5] This allows their anchorage to a gold surface and formation of self-assembled monolayers (diamond-on-gold).

Organic chemistry of diamondoids even extends to pentamantane.[6] The medial position (base) in this molecule (the isomer [1(2,3)4]pentamantane) is calculated to yield a more favorable carbocation than the apical position (top) and simple bromination of pentamantane 1 with bromine exclusively gives the medial bromo derivative 2 which on hydrolysis in water and DMF forms the alcohol 3.

 
Pentamane chemistry

In contrast nitrooxylation of 1 with nitric acid gives the apical nitrate 4 as an intermediate which is hydrolysed to the apical alcohol 5 due to the higher steric demand of the active electrophilic NO−
2HNO+
3 species. This alcohol can react with thionyl bromide to the bromide 6 and in a series of steps (not shown) to the corresponding thiol. Pentamantane can also react with tetrabromomethane and tetra-n-butylammonium bromide (TBABr) in a free radical reaction to the bromide but without selectivity.

Origin and occurrence edit

Diamondoids are found in mature high-temperature petroleum fluids (volatile oils, condensates and wet gases). These fluids can have up to a spoonful of diamondoids per US gallon (3.78 liters). A review by Mello and Moldowan in 2005 showed that although the carbon in diamonds is not biological in origin, the diamondoids found in petroleum are composed of carbon from biological sources. This was determined by comparing the ratios of carbon isotopes present.[7]

Optical and electronic properties edit

The optical absorption for all diamondoids lies deep in the ultraviolet spectral region with optical band gaps around 6 electronvolts and higher.[8] The spectrum of each diamondoid is found to reflect its individual size, shape and symmetry. Due to their well-defined size and structure diamondoids also serve as a model system for electronic structure calculations.[9]

Many of the optoelectronic properties of diamondoids are determined by the difference in the nature of the highest occupied and lowest unoccupied molecular orbitals: the former is a bulk state, whereas the latter is a surface state. As a result, the energy of the lowest unoccupied molecular orbital is roughly independent of the size of the diamondoid.[10][11]

Diamondoids have been found to exhibit a negative electron affinity, making them potentially useful in electron-emission devices.[10][12]

See also edit

References edit

  1. ^ a b Dahl, J. E.; Liu, S. G.; Carlson, R. M. K. (3 January 2003). "Isolation and Structure of Higher Diamondoids, Nanometer-Sized Diamond Molecules". Science. 299 (5603): 96–99. doi:10.1126/science.1078239. PMID 12459548. S2CID 46688135.
  2. ^ Dahl, J. E. P.; Moldowan, J. M.; Peakman, T. M.; Clardy, J. C.; Lobkovsky, E.; Olmstead, M. M.; May, P. W.; Davis, T. J.; Steeds, J. W.; Peters, K. E.; Pepper, A.; Ekuan, A.; Carlson, R. M. K. (2003). "Isolation and Structural Proof of the Large Diamond Molecule, Cyclohexamantane (C26H30)". Angewandte Chemie International Edition. 42 (18): 2040–2044. doi:10.1002/anie.200250794. PMID 12746817.
  3. ^ Burns, W.; McKervey, M. A.; Mitchell, T. R.; Rooney, J. J. (1978). "A New Approach to the Construction of Diamondoid Hydrocarbons. Synthesis of anti-Tetramantane". Journal of the American Chemical Society. 100 (3): 906–911. doi:10.1021/ja00471a041.
  4. ^ Zhang, J.; Zhu, Z.; Feng, Y.; Ishiwata, H.; Miyata, Y.; Kitaura, R.; Dahl, J. E.; Carlson, R. M.; Fokina, N. A.; Schreiner, P. R.; Tománek, D.; Shinohara, H. (Mar 25, 2013). "Evidence of diamond nanowires formed inside carbon nanotubes from diamantane dicarboxylic acid". Angewandte Chemie International Edition. 52 (13): 3717–3721. doi:10.1002/anie.201209192. PMID 23418054.
  5. ^ Tkachenko, Boryslav A.; Fokina, Natalie A.; Chernish, Lesya V.; Dahl, Jeremy E. P.; Liu, Shenggao; Carlson, Robert M. K.; Fokin, Andrey A.; Schreiner, Peter R. (2006). "Functionalized Nanodiamonds Part 3: Thiolation of Tertiary/Bridgehead Alcohols". Organic Letters. 8 (9): 1767–70. doi:10.1021/ol053136g. PMID 16623546.
  6. ^ Fokin, Andrey A.; Schreiner, Peter R.; Fokina, Natalie A.; Tkachenko, Boryslav A.; Hausmann, Heike; Serafin, Michael; Dahl, Jeremy E. P.; Liu, Shenggao; Carlson, Robert M. K. (2006). "Reactivity of [1(2,3)4]Pentamantane (Td-Pentamantane): A Nanoscale Model of Diamond". The Journal of Organic Chemistry. 71 (22): 8532–8540. doi:10.1021/jo061561x. PMID 17064030.
  7. ^ Mello, M. R.; Moldowan, J. M. (2005). "Petroleum: To Be Or Not To Be Abiogenic". Search and Discovery.
  8. ^ Landt, L.; Klünder, K.; Dahl, J. E.; Carlson, R. M. K.; Möller, T.; Bostedt, C. (2009). "Optical Response of Diamond Nanocrystals as a Function of Particle Size, Shape, and Symmetry". Physical Review Letters. 103 (4): 047402. Bibcode:2009PhRvL.103d7402L. doi:10.1103/PhysRevLett.103.047402. PMID 19659398.
  9. ^ Vörös, M.; Gali, A. (2009). "Optical absorption of diamond nanocrystals from ab initio density-functional calculations". Physical Review B. 80 (16): 161411. Bibcode:2009PhRvB..80p1411V. doi:10.1103/PhysRevB.80.161411.
  10. ^ a b Drummond, N. D.; Williamson, A. J.; Needs, R. J.; Galli, G. (2005). "Electron emission from diamondoids: a diffusion quantum Monte Carlo study". Physical Review Letters. 95 (9): 096801–096804. arXiv:0801.0381. Bibcode:2005PhRvL..95i6801D. doi:10.1103/PhysRevLett.95.096801. PMID 16197235. S2CID 16703233.
  11. ^ Willey, T. M.; Bostedt, C.; van Buuren, T.; Dahl, J. E.; Liu, S. G.; Carlson, R. M. K.; Terminello, L. J.; Möller, T. (2005). "Molecular Limits to the Quantum Confinement Model in Diamond Clusters". Physical Review Letters (Submitted manuscript). 95 (11): 113401–113404. Bibcode:2005PhRvL..95k3401W. doi:10.1103/PhysRevLett.95.113401. PMID 16197003.
  12. ^ Yang, W. L.; Fabbri, J. D.; Willey, T. M.; Lee, J. R. I.; Dahl, J. E.; Carlson, R. M. K.; Schreiner, P. R.; Fokin, A. A.; Tkachenko, B. A.; Fokina, N. A.; Meevasana, W.; Mannella, N.; Tanaka, K.; Zhou, X.-J.; van Buuren, T.; Kelly, M. A.; Hussain, Z.; Melosh, N. A.; Shen, Z.-X. (2007). "Monochromatic Electron Photoemission from Diamondoid Monolayers" (PDF). Science. 316 (5830): 1460–1462. Bibcode:2007Sci...316.1460Y. doi:10.1126/science.1141811. PMID 17556579.

External links edit

  • Cluster and Nanocrystal Research Group, Technische Universität Berlin
  • Laser Raman Spectroscopy and Modelling of Diamondoids
  • Electronic and Optical Properties of Diamondoids (free download)
  • Diamondoid Molecules: With Applications in Biomedicine, Materials Science, Nanotechnology & Petroleum Science
  • Diamondoid-functionalized gold nanogaps as sensors for natural, mutated, and epigenetically modified DNA nucleotides

December 20, 2023
diamondoid, chemistry, diamondoids, variants, carbon, cage, molecule, known, adamantane, c10h16, smallest, unit, cage, structure, diamond, crystal, lattice, also, known, nanodiamonds, condensed, adamantanes, include, more, cages, adamantane, diamantane, triama. In chemistry diamondoids are variants of the carbon cage molecule known as adamantane C10H16 the smallest unit cage structure of the diamond crystal lattice Diamondoids also known as nanodiamonds or condensed adamantanes may include one or more cages adamantane diamantane triamantane and higher polymantanes as well as numerous isomeric and structural variants of adamantanes and polymantanes These diamondoids occur naturally in petroleum deposits and have been extracted and purified into large pure crystals of polymantane molecules having more than a dozen adamantane cages per molecule 1 These species are of interest as molecular approximations of the diamond cubic framework terminated with C H bonds Cyclohexamantane may be thought of as a nanometer sized diamond of approximately 5 6 10 22 grams 2 Contents 1 Examples 2 Origin and occurrence 3 Optical and electronic properties 4 See also 5 References 6 External linksExamples edit nbsp Diamondoids from left to right adamantane diamantane triamantane and one isomer of tetramantaneExamples include Adamantane C10H16 Iceane C12H18 BC 8 C14H20 Diamantane C14H20 also diadamantane two face fused cages Triamantane C18H24 also triadamantane Diamantane has four identical faces available for anchoring a new C4H4 unit Isotetramantane C22H28 Triamantane has eight faces on to which a new C4H4 unit can be added resulting in four isomers One of these isomers displays a helical twist and is therefore prochiral The P and M enantiomers have been separated Pentamantane has nine isomers with chemical formula C26H32 and one more pentamantane exists with chemical formula C25H30 Cyclohexamantane C26H30 Super adamantane C30H36 One tetramantane isomer is the largest ever diamondoid prepared by organic synthesis using a keto carbenoid reaction to attach cyclopentane rings 3 Longer diamondoids have been formed from diamantane dicarboxylic acid 4 The first ever isolation of a wide range of diamondoids from petroleum took place in the following steps 1 a vacuum distillation above 345 C the equivalent atmospheric boiling point then pyrolysis at 400 to 450 C in order to remove all non diamondoid compounds diamondoids are thermodynamically very stable and will survive this pyrolysis and then a series of high performance liquid chromatography separation techniques In one study a tetramantane compound is fitted with thiol groups at the bridgehead positions 5 This allows their anchorage to a gold surface and formation of self assembled monolayers diamond on gold Organic chemistry of diamondoids even extends to pentamantane 6 The medial position base in this molecule the isomer 1 2 3 4 pentamantane is calculated to yield a more favorable carbocation than the apical position top and simple bromination of pentamantane 1 with bromine exclusively gives the medial bromo derivative 2 which on hydrolysis in water and DMF forms the alcohol 3 nbsp Pentamane chemistryIn contrast nitrooxylation of 1 with nitric acid gives the apical nitrate 4 as an intermediate which is hydrolysed to the apical alcohol 5 due to the higher steric demand of the active electrophilic NO 2 HNO 3 species This alcohol can react with thionyl bromide to the bromide 6 and in a series of steps not shown to the corresponding thiol Pentamantane can also react with tetrabromomethane and tetra n butylammonium bromide TBABr in a free radical reaction to the bromide but without selectivity Origin and occurrence editDiamondoids are found in mature high temperature petroleum fluids volatile oils condensates and wet gases These fluids can have up to a spoonful of diamondoids per US gallon 3 78 liters A review by Mello and Moldowan in 2005 showed that although the carbon in diamonds is not biological in origin the diamondoids found in petroleum are composed of carbon from biological sources This was determined by comparing the ratios of carbon isotopes present 7 Optical and electronic properties editThe optical absorption for all diamondoids lies deep in the ultraviolet spectral region with optical band gaps around 6 electronvolts and higher 8 The spectrum of each diamondoid is found to reflect its individual size shape and symmetry Due to their well defined size and structure diamondoids also serve as a model system for electronic structure calculations 9 Many of the optoelectronic properties of diamondoids are determined by the difference in the nature of the highest occupied and lowest unoccupied molecular orbitals the former is a bulk state whereas the latter is a surface state As a result the energy of the lowest unoccupied molecular orbital is roughly independent of the size of the diamondoid 10 11 Diamondoids have been found to exhibit a negative electron affinity making them potentially useful in electron emission devices 10 12 See also editOther diamond like compounds Boron nitride Abiogenic petroleum originReferences edit a b Dahl J E Liu S G Carlson R M K 3 January 2003 Isolation and Structure of Higher Diamondoids Nanometer Sized Diamond Molecules Science 299 5603 96 99 doi 10 1126 science 1078239 PMID 12459548 S2CID 46688135 Dahl J E P Moldowan J M Peakman T M Clardy J C Lobkovsky E Olmstead M M May P W Davis T J Steeds J W Peters K E Pepper A Ekuan A Carlson R M K 2003 Isolation and Structural Proof of the Large Diamond Molecule Cyclohexamantane C26H30 Angewandte Chemie International Edition 42 18 2040 2044 doi 10 1002 anie 200250794 PMID 12746817 Burns W McKervey M A Mitchell T R Rooney J J 1978 A New Approach to the Construction of Diamondoid Hydrocarbons Synthesis of anti Tetramantane Journal of the American Chemical Society 100 3 906 911 doi 10 1021 ja00471a041 Zhang J Zhu Z Feng Y Ishiwata H Miyata Y Kitaura R Dahl J E Carlson R M Fokina N A Schreiner P R Tomanek D Shinohara H Mar 25 2013 Evidence of diamond nanowires formed inside carbon nanotubes from diamantane dicarboxylic acid Angewandte Chemie International Edition 52 13 3717 3721 doi 10 1002 anie 201209192 PMID 23418054 Tkachenko Boryslav A Fokina Natalie A Chernish Lesya V Dahl Jeremy E P Liu Shenggao Carlson Robert M K Fokin Andrey A Schreiner Peter R 2006 Functionalized Nanodiamonds Part 3 Thiolation of Tertiary Bridgehead Alcohols Organic Letters 8 9 1767 70 doi 10 1021 ol053136g PMID 16623546 Fokin Andrey A Schreiner Peter R Fokina Natalie A Tkachenko Boryslav A Hausmann Heike Serafin Michael Dahl Jeremy E P Liu Shenggao Carlson Robert M K 2006 Reactivity of 1 2 3 4 Pentamantane Td Pentamantane A Nanoscale Model of Diamond The Journal of Organic Chemistry 71 22 8532 8540 doi 10 1021 jo061561x PMID 17064030 Mello M R Moldowan J M 2005 Petroleum To Be Or Not To Be Abiogenic Search and Discovery Landt L Klunder K Dahl J E Carlson R M K Moller T Bostedt C 2009 Optical Response of Diamond Nanocrystals as a Function of Particle Size Shape and Symmetry Physical Review Letters 103 4 047402 Bibcode 2009PhRvL 103d7402L doi 10 1103 PhysRevLett 103 047402 PMID 19659398 Voros M Gali A 2009 Optical absorption of diamond nanocrystals from ab initio density functional calculations Physical Review B 80 16 161411 Bibcode 2009PhRvB 80p1411V doi 10 1103 PhysRevB 80 161411 a b Drummond N D Williamson A J Needs R J Galli G 2005 Electron emission from diamondoids a diffusion quantum Monte Carlo study Physical Review Letters 95 9 096801 096804 arXiv 0801 0381 Bibcode 2005PhRvL 95i6801D doi 10 1103 PhysRevLett 95 096801 PMID 16197235 S2CID 16703233 Willey T M Bostedt C van Buuren T Dahl J E Liu S G Carlson R M K Terminello L J Moller T 2005 Molecular Limits to the Quantum Confinement Model in Diamond Clusters Physical Review Letters Submitted manuscript 95 11 113401 113404 Bibcode 2005PhRvL 95k3401W doi 10 1103 PhysRevLett 95 113401 PMID 16197003 Yang W L Fabbri J D Willey T M Lee J R I Dahl J E Carlson R M K Schreiner P R Fokin A A Tkachenko B A Fokina N A Meevasana W Mannella N Tanaka K Zhou X J van Buuren T Kelly M A Hussain Z Melosh N A Shen Z X 2007 Monochromatic Electron Photoemission from Diamondoid Monolayers PDF Science 316 5830 1460 1462 Bibcode 2007Sci 316 1460Y doi 10 1126 science 1141811 PMID 17556579 External links editCluster and Nanocrystal Research Group Technische Universitat Berlin Molecular Diamond Technologies Chevron Texaco Nanotechnology and the arrival of the Diamond Age Laser Raman Spectroscopy and Modelling of Diamondoids Electronic and Optical Properties of Diamondoids free download Diamondoid Molecules With Applications in Biomedicine Materials Science Nanotechnology amp Petroleum Science Diamondoid functionalized gold nanogaps as sensors for natural mutated and epigenetically modified DNA nucleotides Retrieved from https en wikipedia org w index php title Diamondoid amp oldid 1184075609, wikipedia, wiki, book, books, library,

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